Systems and methods for anisotropic material breakthrough

ABSTRACT

Processing methods may be performed to remove unwanted materials from a substrate, such as a native oxide material. The methods may include forming an inert plasma within a processing region of a processing chamber. Effluents of the inert plasma may be utilized to modify a surface of an exposed material on a semiconductor substrate within the processing region of the semiconductor chamber. A remote plasma may be formed from a fluorine-containing precursor to produce plasma effluents. The methods may include flowing the plasma effluents to the processing region of the semiconductor processing chamber. The methods may also include removing the modified surface of the exposed material from the semiconductor substrate.

TECHNICAL FIELD

The present technology relates to semiconductor systems, processes, and equipment. More specifically, the present technology relates to systems and methods for anisotropically removing oxide or nitride materials on a wafer surface.

BACKGROUND

Integrated circuits are made possible by processes which produce intricately patterned material layers on substrate surfaces. Producing patterned material on a substrate requires controlled methods for removal of exposed material. Chemical etching is used for a variety of purposes including transferring a pattern in photoresist into underlying layers, thinning layers, or thinning lateral dimensions of features already present on the surface. Often it is desirable to have an etch process that etches one material faster than another facilitating, for example, a pattern transfer process. Such an etch process is said to be selective to the first material. As a result of the diversity of materials, circuits, and processes, etch processes have been developed with a selectivity towards a variety of materials.

Etch processes may be termed wet or dry based on the materials used in the process. A wet HF etch preferentially removes silicon oxide over other dielectrics and materials. However, wet processes may have difficulty penetrating some constrained trenches and also may sometimes deform the remaining material. Dry etches produced in local plasmas formed within the substrate processing region can penetrate more constrained trenches and exhibit less deformation of delicate remaining structures. However, local plasmas may damage the substrate through the production of electric arcs as they discharge.

Thus, there is a need for improved systems and methods that can be used to produce high quality devices and structures. These and other needs are addressed by the present technology.

SUMMARY

Processing methods may be performed to remove unwanted materials from a substrate, such as a native oxide over a material such as a silicon-containing material. The methods may include forming an inert plasma within a processing region of a processing chamber. Effluents of the inert plasma may be utilized to modify a surface of an exposed material on a semiconductor substrate within the processing region of the semiconductor chamber. A remote plasma may be formed from a fluorine-containing precursor to produce plasma effluents. The methods may include flowing the plasma effluents to the processing region of the semiconductor processing chamber. The methods may also include removing the modified surface of the exposed material from the semiconductor substrate.

During the modification operation, the inert plasma may include or be composed of a hydrogen plasma. The inert plasma may be formed from a bias power below about 100 W. In embodiments, the surface of the exposed material on the semiconductor substrate may be modified to a depth from the exposed surface within the semiconductor substrate of less than about 5 nm. A pressure within the semiconductor processing chamber while forming the inert plasma and during the modifying may be maintained below about 500 mTorr.

The remote plasma may be formed in a region of the semiconductor processing chamber fluidly isolated from the processing region of the semiconductor processing chamber or may be formed in a remote plasma unit fluidly coupled with the semiconductor processing chamber. The semiconductor substrate may be maintained at a temperature above or about 80° C. during the removal of the modified surface of the exposed material. Removing the modified surface of the exposed material may expose an unmodified portion of the material, and an etching selectivity of a modified portion of the material to the unmodified portion of the material may be greater than or about 100:1, greater than or about 1,000:1, or higher. The exposed material on the semiconductor substrate may include an oxide material located proximate a polysilicon material positioned along the semiconductor substrate. In embodiments, the remote plasma may be additionally formed from a hydrogen-containing precursor. Also, in embodiments each operation of the etching method may be repeated in at least one additional cycle, and a total removal after all cycles may be less than 10 nm.

The present technology may also include etching methods for removing silicon oxide materials. The methods may include forming an inert plasma within a processing region of a semiconductor processing chamber. The methods may include modifying an exposed region of silicon oxide on a semiconductor substrate within the processing region of the semiconductor processing chamber with effluents of the inert plasma. The methods may include contacting the modified silicon oxide with plasma effluents of a fluorine-containing precursor. The methods may further include etching the modified silicon oxide. In embodiments the modifying, contacting, and etching may all be performed in a single semiconductor processing chamber.

In embodiments, the etching may be performed at a temperature of about 90° C. The plasma effluents of the fluorine-containing precursor may be formed in a remote region of the semiconductor processing chamber fluidly coupled with, and physically separated from, the processing region of the semiconductor processing chamber. The plasma effluents of the fluorine-containing precursor may be produced by a capacitively-coupled plasma at a power level less than or about 100 W. In embodiments, the modified silicon oxide may be additionally contacted with a hydrogen-containing precursor. The hydrogen-containing precursor may bypass the remote region of the semiconductor processing chamber. The hydrogen-containing precursor may interact with the plasma effluents of the fluorine-containing precursor subsequent to the plasma effluents of the fluorine-containing precursor exiting the remote region of the semiconductor processing chamber.

The present technology also includes methods of etching a material along a mandrel. The methods may include forming an inert plasma within a processing region of a semiconductor processing chamber. The inert plasma may include a hydrogen plasma formed by a bias power of less than about 100 W. The methods may also include modifying an exposed region of silicon oxide on a semiconductor substrate within the processing region of the semiconductor processing chamber with effluents of the inert plasma. The exposed region of silicon oxide may be or include a material positioned about a silicon mandrel formed on a substrate. Also, during the modification operation, a pressure within the semiconductor processing chamber may be maintained below about 1 Torr.

The methods may also include forming a plasma of a fluorine-containing precursor in a remote region of the semiconductor processing chamber that is separated from the processing region of the semiconductor processing chamber by a showerhead. The methods may include contacting the modified silicon oxide with plasma effluents of the fluorine-containing precursor. Additionally, the methods may include etching the modified silicon oxide at a temperature of about 90° C. In embodiments, the modifying, contacting, and etching may all be performed in the same semiconductor processing chamber. In some embodiments no solid byproducts are produced during the etching. The remote region of the semiconductor processing chamber may be a region defined within the semiconductor processing chamber in embodiments. Additionally, the remote region of the semiconductor processing chamber may be a region external to the semiconductor processing chamber, but fluidly coupled with an inlet to the semiconductor processing chamber. The methods may also include annealing modified silicon oxide remaining subsequent the etching operation. The annealing may include contacting the modified silicon oxide with an inert gas heated to a temperature above a temperature of the substrate.

Such technology may provide numerous benefits over conventional systems and techniques. For example, a native oxide formed in previous operations can be selectively removed from an underlying silicon-containing material. Additionally, the virtually infinite selectivity with respect to oxide may allow treatment to be performed on reduced thickness materials while maintaining lateral dimensions of surrounding barriers and liners. These and other embodiments, along with many of their advantages and features, are described in more detail in conjunction with the below description and attached figures.

BRIEF DESCRIPTION OF THE DRAWINGS

A further understanding of the nature and advantages of the disclosed technology may be realized by reference to the remaining portions of the specification and the drawings.

FIG. 1 shows a top plan view of an exemplary processing system according to embodiments of the present technology.

FIG. 2A shows a schematic cross-sectional view of an exemplary processing chamber according to embodiments of the present technology.

FIG. 2B shows a detailed view of an exemplary showerhead according to embodiments of the present technology.

FIG. 3 shows a bottom plan view of an exemplary showerhead according to embodiments of the present technology.

FIG. 4 shows selected operations in an etching method according to embodiments of the present technology.

FIGS. 5A-5C illustrate cross-sectional views of substrate materials on which selected operations are being performed according to embodiments of the present technology.

Several of the figures are included as schematics. It is to be understood that the figures are for illustrative purposes, and are not to be considered of scale unless specifically stated to be of scale. Additionally, as schematics, the figures are provided to aid comprehension and may not include all aspects or information compared to realistic representations, and may include exaggerated material for illustrative purposes.

In the appended figures, similar components and/or features may have the same reference label. Further, various components of the same type may be distinguished by following the reference label by a letter that distinguishes among the similar components. If only the first reference label is used in the specification, the description is applicable to any one of the similar components having the same first reference label irrespective of the letter.

DETAILED DESCRIPTION

The present technology includes systems and components for semiconductor processing of small pitch features. As line pitch is reduced, standard lithography processes may be limited, and alternative mechanisms may be used in patterning. During one such patterning operation, spacers may be removed with a reactive ion etching process, such as in self-aligned double or quadruple patterning. After the etching, an ashing process may be performed to strip the carbon polymer. This process may produce oxide, such as a native oxide over exposed mandrels, such as polysilicon mandrels. The process of removing the oxide is termed breakthrough in which the oxide is removed to expose the underlying polysilicon mandrels, which may be dummy polysilicon. However, such a process may etch barrier, liner, and spacer materials that may also be oxide from the sidewalls about the dummy silicon. As feature size reduces, the critical dimensions of these barriers may be overly reduced, which may cause device issues such as shorting or device failures.

Conventional technologies have struggled with this removal because the etching processes used are often isotropic, and thus may be prone to removing liners, spacers, and other barrier materials from the sidewalls in between silicon mandrels. Additionally, these and other etching processes may also damage underlying hardmask layers, which may also be relatively thin. Another issue with further using reactive ion etching to remove the oxide materials is that the process may include more chamber switching between operations, which if the movement breaks vacuum, may further produce native oxide over the polysilicon. The present technology, however, takes advantage of a single chamber capable of both surface modification as well as etching capabilities to affect material quality, etch rates, and selectivity. By modifying or damaging the native oxide, removal can be performed under etching conditions that may be less suitable for standard film removal. These techniques may not only remove undesired materials, but may perform the removal in a controlled fashion that limits overall material effects. Accordingly, the techniques explained may be suitable for a variety of semiconductor processes across industry by allowing limited removal at highly selective rates. For example, along with native oxide removal, these techniques may be used in dummy polysilicon pull-off, strained source drain, and many other modification and removal processes.

Although the remaining disclosure will routinely identify specific etching processes utilizing the disclosed technology, it will be readily understood that the systems and methods are equally applicable to deposition and cleaning processes as may occur in the described chambers. Accordingly, the technology should not be considered to be so limited as for use with etching processes alone.

FIG. 1 shows a top plan view of one embodiment of a processing system 100 of deposition, etching, baking, and curing chambers according to embodiments. In the figure, a pair of front opening unified pods (FOUPs) 102 supply substrates of a variety of sizes that are received by robotic arms 104 and placed into a low pressure holding area 106 before being placed into one of the substrate processing chambers 108 a-f, positioned in tandem sections 109 a-c. A second robotic arm 110 may be used to transport the substrate wafers from the holding area 106 to the substrate processing chambers 108 a-f and back. Each substrate processing chamber 108 a-f, can be outfitted to perform a number of substrate processing operations including the dry etch processes described herein in addition to cyclical layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, pre-clean, degas, orientation, and other substrate processes.

The substrate processing chambers 108 a-f may include one or more system components for depositing, annealing, curing and/or etching a dielectric film on the substrate wafer. In one configuration, two pairs of the processing chambers, e.g., 108 c-d and 108 e-f, may be used to deposit dielectric material on the substrate, and the third pair of processing chambers, e.g., 108 a-b, may be used to etch the deposited dielectric. In another configuration, all three pairs of chambers, e.g., 108 a-f, may be configured to etch a dielectric film on the substrate. Any one or more of the processes described may be carried out in chamber(s) separated from the fabrication system shown in different embodiments. It will be appreciated that additional configurations of deposition, etching, annealing, and curing chambers for dielectric films are contemplated by system 100.

FIG. 2A shows a cross-sectional view of an exemplary process chamber system 200 with partitioned plasma generation regions within the processing chamber. During film etching, e.g., titanium nitride, tantalum nitride, tungsten, silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, etc., a process gas may be flowed into the first plasma region 215 through a gas inlet assembly 205. A remote plasma system (RPS) 201 may optionally be included in the system, and may process a first gas which then travels through gas inlet assembly 205. The inlet assembly 205 may include two or more distinct gas supply channels where the second channel (not shown) may bypass the RPS 201, if included.

A cooling plate 203, faceplate 217, ion suppressor 223, showerhead 225, and a substrate support 265, having a substrate 255 disposed thereon, are shown and may each be included according to embodiments. The pedestal 265 may have a heat exchange channel through which a heat exchange fluid flows to control the temperature of the substrate, which may be operated to heat and/or cool the substrate or wafer during processing operations. The wafer support platter of the pedestal 265, which may comprise aluminum, ceramic, or a combination thereof, may also be resistively heated in order to achieve relatively high temperatures, such as from up to or about 100° C. to above or about 1100° C., using an embedded resistive heater element.

The faceplate 217 may be pyramidal, conical, or of another similar structure with a narrow top portion expanding to a wide bottom portion. The faceplate 217 may additionally be flat as shown and include a plurality of through-channels used to distribute process gases. Plasma generating gases and/or plasma excited species, depending on use of the RPS 201, may pass through a plurality of holes, shown in FIG. 2B, in faceplate 217 for a more uniform delivery into the first plasma region 215.

Exemplary configurations may include having the gas inlet assembly 205 open into a gas supply region 258 partitioned from the first plasma region 215 by faceplate 217 so that the gases/species flow through the holes in the faceplate 217 into the first plasma region 215. Structural and operational features may be selected to prevent significant backflow of plasma from the first plasma region 215 back into the supply region 258, gas inlet assembly 205, and fluid supply system 210. The faceplate 217, or a conductive top portion of the chamber, and showerhead 225 are shown with an insulating ring 220 located between the features, which allows an AC potential to be applied to the faceplate 217 relative to showerhead 225 and/or ion suppressor 223. The insulating ring 220 may be positioned between the faceplate 217 and the showerhead 225 and/or ion suppressor 223 enabling a capacitively coupled plasma (CCP) to be formed in the first plasma region. A baffle (not shown) may additionally be located in the first plasma region 215, or otherwise coupled with gas inlet assembly 205, to affect the flow of fluid into the region through gas inlet assembly 205.

The ion suppressor 223 may comprise a plate or other geometry that defines a plurality of apertures throughout the structure that are configured to suppress the migration of ionically-charged species out of the first plasma region 215 while allowing uncharged neutral or radical species to pass through the ion suppressor 223 into an activated gas delivery region between the suppressor and the showerhead. In embodiments, the ion suppressor 223 may comprise a perforated plate with a variety of aperture configurations. These uncharged species may include highly reactive species that are transported with less reactive carrier gas through the apertures. As noted above, the migration of ionic species through the holes may be reduced, and in some instances completely suppressed. Controlling the amount of ionic species passing through the ion suppressor 223 may advantageously provide increased control over the gas mixture brought into contact with the underlying wafer substrate, which in turn may increase control of the deposition and/or etch characteristics of the gas mixture. For example, adjustments in the ion concentration of the gas mixture can significantly alter its etch selectivity, e.g., SiNx:SiOx etch ratios, Si:SiOx etch ratios, etc. In alternative embodiments in which deposition is performed, it can also shift the balance of conformal-to-flowable style depositions for dielectric materials.

The plurality of apertures in the ion suppressor 223 may be configured to control the passage of the activated gas, i.e., the ionic, radical, and/or neutral species, through the ion suppressor 223. For example, the aspect ratio of the holes, or the hole diameter to length, and/or the geometry of the holes may be controlled so that the flow of ionically-charged species in the activated gas passing through the ion suppressor 223 is reduced. The holes in the ion suppressor 223 may include a tapered portion that faces the plasma excitation region 215, and a cylindrical portion that faces the showerhead 225. The cylindrical portion may be shaped and dimensioned to control the flow of ionic species passing to the showerhead 225. An adjustable electrical bias may also be applied to the ion suppressor 223 as an additional means to control the flow of ionic species through the suppressor.

The ion suppressor 223 may function to reduce or eliminate the amount of ionically charged species traveling from the plasma generation region to the substrate. Uncharged neutral and radical species may still pass through the openings in the ion suppressor to react with the substrate. It should be noted that the complete elimination of ionically charged species in the reaction region surrounding the substrate may not be performed in embodiments. In certain instances, ionic species are intended to reach the substrate in order to perform the etch and/or deposition process. In these instances, the ion suppressor may help to control the concentration of ionic species in the reaction region at a level that assists the process.

Showerhead 225 in combination with ion suppressor 223 may allow a plasma present in first plasma region 215 to avoid directly exciting gases in substrate processing region 233, while still allowing excited species to travel from chamber plasma region 215 into substrate processing region 233. In this way, the chamber may be configured to prevent the plasma from contacting a substrate 255 being etched. This may advantageously protect a variety of intricate structures and films patterned on the substrate, which may be damaged, dislocated, or otherwise warped if directly contacted by a generated plasma. Additionally, when plasma is allowed to contact the substrate or approach the substrate level, the rate at which oxide species etch may increase. Accordingly, if an exposed region of material is oxide, this material may be further protected by maintaining the plasma remotely from the substrate.

The processing system may further include a power supply 240 electrically coupled with the processing chamber to provide electric power to the faceplate 217, ion suppressor 223, showerhead 225, and/or pedestal 265 to generate a plasma in the first plasma region 215 or processing region 233. The power supply may be configured to deliver an adjustable amount of power to the chamber depending on the process performed. Such a configuration may allow for a tunable plasma to be used in the processes being performed. Unlike a remote plasma unit, which is often presented with on or off functionality, a tunable plasma may be configured to deliver a specific amount of power to the plasma region 215. This in turn may allow development of particular plasma characteristics such that precursors may be dissociated in specific ways to enhance the etching profiles produced by these precursors.

A plasma may be ignited either in chamber plasma region 215 above showerhead 225 or substrate processing region 233 below showerhead 225. In embodiments, the plasma formed in substrate processing region 233 may be a DC biased plasma formed with the pedestal acting as an electrode. Plasma may be present in chamber plasma region 215 to produce the radical precursors from an inflow of, for example, a fluorine-containing precursor or other precursor. An AC voltage typically in the radio frequency (RF) range may be applied between the conductive top portion of the processing chamber, such as faceplate 217, and showerhead 225 and/or ion suppressor 223 to ignite a plasma in chamber plasma region 215 during deposition. An RF power supply may generate a high RF frequency of 13.56 MHz but may also generate other frequencies alone or in combination with the 13.56 MHz frequency.

FIG. 2B shows a detailed view 253 of the features affecting the processing gas distribution through faceplate 217. As shown in FIGS. 2A and 2B, faceplate 217, cooling plate 203, and gas inlet assembly 205 intersect to define a gas supply region 258 into which process gases may be delivered from gas inlet 205. The gases may fill the gas supply region 258 and flow to first plasma region 215 through apertures 259 in faceplate 217. The apertures 259 may be configured to direct flow in a substantially unidirectional manner such that process gases may flow into processing region 233, but may be partially or fully prevented from backflow into the gas supply region 258 after traversing the faceplate 217.

The gas distribution assemblies such as showerhead 225 for use in the processing chamber section 200 may be referred to as dual channel showerheads (DCSH) and are additionally detailed in the embodiments described in FIG. 3. The dual channel showerhead may provide for etching processes that allow for separation of etchants outside of the processing region 233 to provide limited interaction with chamber components and each other prior to being delivered into the processing region.

The showerhead 225 may comprise an upper plate 214 and a lower plate 216. The plates may be coupled with one another to define a volume 218 between the plates. The coupling of the plates may be so as to provide first fluid channels 219 through the upper and lower plates, and second fluid channels 221 through the lower plate 216. The formed channels may be configured to provide fluid access from the volume 218 through the lower plate 216 via second fluid channels 221 alone, and the first fluid channels 219 may be fluidly isolated from the volume 218 between the plates and the second fluid channels 221. The volume 218 may be fluidly accessible through a side of the gas distribution assembly 225.

FIG. 3 is a bottom view of a showerhead 325 for use with a processing chamber according to embodiments. Showerhead 325 may correspond with the showerhead 225 shown in FIG. 2A. Through-holes 365, which show a view of first fluid channels 219, may have a plurality of shapes and configurations in order to control and affect the flow of precursors through the showerhead 225. Small holes 375, which show a view of second fluid channels 221, may be distributed substantially evenly over the surface of the showerhead, even amongst the through-holes 365, and may help to provide more even mixing of the precursors as they exit the showerhead than other configurations.

FIG. 4 illustrates an etching method 400 that may be performed, for example, in the chamber 200 as previously described. Method 400 may include one or more operations prior to the initiation of the method, including front end processing, deposition, etching, polishing, cleaning, or any other operations that may be performed prior to the described operations. For example, in an exemplary breakthrough process on a substrate, spacer etching may occur with a reactive ion etching process, and a following ashing process may have been performed. The ashing process may be performed to remove residual carbon polymer from the reactive ion etching. The processed substrate, which may be a semiconductor wafer of any size, may be positioned within a chamber for the method 400, and may include a native oxide layer overlying a second material which may include a silicon-containing material such as polysilicon. In embodiments the operations of method 400 may be performed in multiple chambers depending on the operations being performed. Additionally, in embodiments the entire method 400 may be performed in a single chamber to reduce queue times, contamination issues, and vacuum break. Subsequent operations to those discussed with respect to method 400 may also be performed in the same chamber or in different chambers as would be readily appreciated by the skilled artisan, and may be discussed further below.

Method 400 may include forming an inert plasma within a processing region of a semiconductor processing chamber at operation 405. A substrate may already be positioned within the chamber prior to operation 405 as discussed above. With reference to chamber 200 for illustration purposes only, the plasma may be formed or generated in region 233, or within a region defined at least in part by the substrate support pedestal. Such a plasma is similarly understood to be a wafer-level plasma. The effluents of the inert plasma may be utilized in method 400 for modifying a surface of an exposed material on a semiconductor substrate at operation 410. The substrate may be within or housed in the processing region of the semiconductor processing chamber.

A remote plasma may be formed at operation 415 to produce plasma effluents, and the remote plasma may include or be composed of a fluorine-containing precursor. In embodiments, the plasma utilized in operation 415 may also be formed at the wafer level, but a remote plasma may reduce a sputtering component at the wafer and from the chamber components. The plasma effluents may be flowed through the processing chamber to the processing region of the semiconductor processing chamber where the substrate is housed at operation 420. Upon contacting the modified surface, the plasma effluents may remove the modified surface of the exposed material from the semiconductor substrate at operation 425.

The modifying and removal operations of method 400 may allow a controlled removal of unwanted materials, such as a native oxide as described previously. The operations may also be well suited for any size features, including small pitch features, or the width between successive materials, such as mandrels, for example, of less than or about 50 nm, less than or about 25 nm, less than or about 20 nm, less than or about 15 nm, less than or about 12 nm, less than or about 10 nm, less than or about 9 nm, less than or about 8 nm, less than or about 7 nm, less than or about 6 nm, less than or about 5 nm, less than or about 4 nm, less than or about 3 nm, less than or about 2 nm, less than or about 1 nm, or smaller. The modifying and removal operations may be performed successively in multiple chambers or in a single chamber, such as, for example, chamber 200, that may produce both wafer-level plasmas and remote plasmas within the chamber, or in association with the chamber.

The modifying operation 410 may involve an inert plasma of one or more materials. The material used to produce the plasma may be one or more noble materials including helium, neon, argon, krypton, xenon, or radon. The material used to produce the plasma may also be additional materials or precursors that may have limited chemical activity or be unreactive with the exposed material on the semiconductor surface being modified. Chemically reactive materials may also be utilized, which may include oxygen and/or hydrogen-containing materials including diatomic hydrogen, ammonia, or other precursors including hydrogen. For example, hydrogen may be used in operation 410, and in embodiments the inert plasma may either comprise or consist of a hydrogen plasma. The hydrogen plasma may be generated from any number of hydrogen containing materials or mixtures, and may be formed exclusively of hydrogen (H₂) in embodiments. The modifying operation may involve a form of bombardment of the material to be removed. With hydrogen being a small, light material, it may be less likely to sputter the material at which it is being directed than heavier materials such as, for example, helium.

The plasma formed from the inert precursor may be a bias plasma providing directional flow of plasma effluents to the substrate. The plasma may be a low-level plasma to limit the amount of bombardment, sputtering, and surface modification. In embodiments the plasma power may be less than or about 300 W, less than or about 250 W, less than or about 200 W, less than or about 150 W, less than or about 100 W, less than or about 75 W, less than or about 50 W, or less than or about 25 W. By utilizing a plasma power that is, for example, about 75 W, the depth of penetration of the plasma effluents may be limited. For example, modification operations as described, may allow the surface of the exposed material on the semiconductor substrate to be modified to a depth from the exposed surface within the semiconductor substrate of less than or about 5 nm, and may allow modification of the surface of materials to a depth of less than or about 4 nm, less than or about 3 nm, less than or about 2 nm, or less than or about 1 nm. For example, by utilizing the low-level plasma, such as at about 75 W, and a relatively light precursor such as hydrogen, the saturation depth of penetration may be around 1-3 nm in embodiments. The modification operation may be relatively or completely insensitive to temperature and material, and may modify or damage exposed regions of nitride, oxide, or polysilicon almost equally.

The pressure within the processing chamber may be controlled during the modification operation 410 as well. For example, while forming the inert plasma and performing the modification operation, the pressure within the processing chamber may be maintained below or about 1 Torr. Additionally, in embodiments, the pressure within the processing chamber may be maintained below or about 750 mTorr, below or about 600 mTorr, below or about 500 mTorr, below or about 400 mTorr, below or about 300 mTorr, below or about 250 mTorr, below or about 200 mTorr, below or about 150 mTorr, below or about 100 mTorr, below or about 80 mTorr, below or about 60 mTorr, below or about 50 mTorr, below or about 40 mTorr, below or about 30 mTorr, below or about 20 mTorr, below or about 10 mTorr, or lower. The pressure within the chamber may affect the directionality of the modification operation 410. For example, as pressure is increased, the modification process may become more isotropic, and as the pressure is reduced, the modification process may become more anisotropic. Thus, as pressure is increased, liner, barrier, spacer, or other materials may begin to be treated as well, which after removal can remove material beyond what was originally desired in certain operations. Accordingly, in embodiments the pressure may be maintained around 250 mTorr to about 300 mTorr, for example, to maintain a relatively or substantially anisotropic profile of the modification operation.

The plasma utilized in the removal operation may be formed remotely from the processing region of the semiconductor processing chamber. For example, the plasma may be formed in a region of the semiconductor processing chamber that is fluidly isolated from the processing region of the semiconductor processing chamber. Thus, the region may be physically separated from the processing region, while being fluidly coupled with the processing region. For example, in the exemplary chamber of FIG. 2, the remote plasma may be generated in region 215, which is separated from the processing region by showerhead 225. Additionally, the remote plasma may be formed in a remote plasma unit, such as an RPS unit that is separate from the chamber, but fluidly coupled with the chamber to deliver plasma effluents into the chamber, such as through a lid, top plate, or showerhead.

The remote plasma may be formed from one or more precursors including a fluorine-containing precursor. The fluorine-containing precursor may include one or more materials including NF₃, HF, F₂, CF₄, CHF₃, C₂F₆, C₃F₆, BrF₃, ClF₃, SF₆, or additional fluorine-substituted hydrocarbons, or fluorine-containing materials. The fluorine-containing precursor may be flowed into the remote plasma region to generate plasma effluents, such as fluorine-containing plasma effluents. A source of hydrogen may also be incorporated as an etchant precursor, and may include hydrogen, ammonia, or any other incompletely substituted hydrocarbon, or other hydrogen-containing material. The source of hydrogen, such as ammonia, for example, may be delivered with the fluorine-containing precursor into the remote plasma region during plasma formation, and thus the plasma effluents may also include hydrogen-containing plasma effluents. The source of hydrogen may also bypass the remote plasma region and be delivered into the processing region where it may interact with the fluorine-containing plasma effluents. In either scenario, the plasma effluents may be delivered to the processing region of the semiconductor processing chamber where they may contact or interact with the modified material on the semiconductor substrate.

As previously discussed, in embodiments the exposed material may include a native oxide located proximate or about a polysilicon mandrel, which may be positioned along a semiconductor substrate. The precursors and plasma effluents may be effective at removing oxide and/or nitride in various semiconductor processes. Selective removal, however, may be affected by processing temperatures. Lower chamber temperatures may allow increased etching of one or more materials. In processes utilizing a fluorine-containing precursor and also a hydrogen-containing precursor to etch oxide materials, the process may involve performing an etch with plasma effluents, or with alternative precursors such as HF, at a low temperature, such as below about 50° C. or lower, to form solid byproducts on the surface of the material being removed. The procedure may then involve heating the materials above around 100° C. in order to sublimate the solid byproducts, which may include ammonium fluorosilicate, for example.

The present technology, however, may perform the removal process at a semiconductor substrate or semiconductor chamber temperature of above or about 50° C., above or about 60° C., above or about 70° C., above or about 80° C., above or about 90° C., above or about 100° C., above or about 110° C., above or about 120° C., above or about 130° C., above or about 140° C., or above or about 150° C. An etching process utilizing the precursors discussed above may have limited capability, or may not etch certain materials at all at a temperature of about 90° C. to about 100° C., for example. While conventional technologies may avoid such temperatures as they may prevent the desired removal, the present technology can utilize this benefit to provide a self-limiting stop on the etching operation. Although unmodified oxide and nitride materials may not etch with the removal process described at a temperature of 90° C., the modified materials produced may etch at a sufficient rate to remove the unwanted materials, such as the native oxide discussed previously.

Thus, once the modified portion of the exposed materials has been removed, the underlying unmodified materials may not etch, or may have limited etching, and may effectively halt the etching process. In this way, minute amounts of material may be removed without overly attacking thin semiconductor layers or small pitch features, and may maintain critical dimensions of spacers, liners, and other barrier materials. Accordingly, in embodiments, removing the modified surface of the exposed material may expose an unmodified portion of the material. An etching selectivity of a modified portion of the material to an unmodified portion of the material may be greater than or about 10:1. Depending on the material being etched, an etching selectivity of a modified portion of the material to an unmodified portion of the material may be greater than or about 20:1, 40:1, 100:1, 1,000:1, 10,000:1, up to about 1:0 at which point the modified portion of the material etches, but an unmodified portion of the material does not etch. The modification operation may produce an amount of dangling bonds and reactive sites for the modified material, which may allow the removal operation to occur under conditions at which the removal may not otherwise occur, or may occur at substantially reduced rates and selectivities for unmodified materials.

As previously explained, the modification operations may be performed at a relatively low plasma power level to create a depth of penetration within the exposed material surfaces of a few nanometers or less, such as about 1 nm to about 2 nm. Because the removal operation can be limited to essentially only remove modified surfaces, or have limited impact on unmodified surfaces, the removal operation may be limited to the modified region, and thus remove about 1 nm, about 2 nm, about 3 nm, or about 4 nm of material. The modification operation may have a saturation depth of about 1 nm in embodiments, but an amount of modification or penetration may occur to up to 2 nm, up to 3 nm, or up to 4 nm, although the saturation depth may be much less. However, the removal operation may continue to etch partially modified regions of material, and thus the removal operation may remove slightly more material than the saturation depth of the modification.

To ensure removal of all native oxide or unwanted material from a substrate, the modification and removal operations may be performed in cycles to allow removal to a depth beyond the typical saturation depth of the modification operation. Accordingly, in embodiments, method 400 may be performed for 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, or more in order to fully remove a material from a substrate. For native oxide removal, the fine-tune control over the material removal based on a saturation depth of the modification operation may allow about 1 nm, about 2 nm, about 3 nm, or about 4 nm to be removed each cycle.

In this way, within 1 cycle, within 2 cycles, within 3 cycles, or within about 4 cycles the entire native oxide may be removed from the substrate at a total removal after all cycles of less than or about 20 nm, less than or about 15 nm, less than or about 12 nm, less than or about 11 nm, less than or about 10 nm, less than or about 9 nm, less than or about 8 nm, less than or about 7 nm, less than or about 6 nm, less than or about 5 nm, less than or about 4 nm, less than or about 3 nm, less than or about 2 nm, or less than or about 1 nm. The operations are being discussed with respect to a limited amount of removal, but the techniques can also be used to remove additional material by, for example, causing the modification to occur to a lower depth, increasing the number of cycles, or by adjusting etching parameters including temperature. However, for limiting the amount of removal in many semiconductor processing operations, the low-power bias plasma with precursors such as previously discussed may allow limited material to be removed with each cycle.

Additional operations may be performed subsequent method 400, or in between cycles of method 400. In exemplary embodiments, the methods may also include annealing the modified surface at operation 430. The polysilicon mandrels may be formed over a hard mask, which can include any known hard mask materials including oxides and nitrides of various materials, such as silicon nitride, titanium nitride, or other metal oxides or nitrides. This hard mask layer may be relatively thin as well, and may be a few nanometers in thickness. Because the hard mask is formed across the underlying substrate, the hard mask may also be exposed to the modification and etching operations, and it may be at least partially etched as well. By utilizing a low plasma power, and because the modification may occur in a top down operation, the modification may not occur to a similar depth as with the native oxide, and may occur to a lesser depth than with the native oxide. The time for dosing the precursors may also limit the amount of hard mask removal in each cycle. Additionally, performing an anneal in between operations may further limit the amount of hard mask removal.

Removal operation 425 may include dosing precursors as discussed previously to remove the modified native oxide. The dose may be limited to less than one minute in embodiments to reduce the amount of removal of the hard mask. In some embodiments the dosing may be limited to less than or about 50 seconds, less than or about 40 seconds, less than or about 30 seconds, less than or about 20 seconds, less than or about 10 seconds, less than or about 5 seconds, or less in embodiments. Dosing intervals below or about 10 seconds to about 15 seconds may limit the amount of interaction with the hard mask. After the removal has occurred, there may still be a tailing effect of the modified surfaces, and an amount of modification may still be present on the exposed surfaces of native oxide and hard mask in between each cycle. This may increase etching in later cycles, or may increase the amount of hard mask removed each cycle.

In some embodiments, the substrate may be raised towards a heated showerhead to perform an anneal on the modified structure to at least partially heal the modification in between cycles of method 400. Because the removal operation 425 may occur to a lesser extent with a hard mask, the anneal may further cure the hard mask in between cycles, which may further limit overall removal of the hard mask layer. In some embodiments the anneal may additionally or alternatively include flowing a precursor towards the substrate. For example, helium or other inert precursors may be flowed towards the substrate that may or may not be raised towards a heated showerhead. The precursor may be heated by the showerhead as well, and may then contact or interact with residual modified materials to anneal the remaining modified portions, which may heal the modification to re-form the material layer. Additionally, although the amount of material removal may be limited in the present technology, it is possible that particulates may be formed during the etching operations. By performing the anneal, volatile reaction products may also be removed from the surface of the substrate if they exist.

Method 400 may then be performed in one or more additional cycles to remove additional native oxide, while limiting the amount of hard mask and other material removal from the substrate. Due to the directionality of the modification operations and the selectivity of the removal operations of the present technology, a native oxide may be removed from an underlying material while limiting the amount of sidewall barrier, liner, and spacer removal, as well as limiting the amount of underlying hard mask or other material removal. For example, the amount of sidewall materials that may be removed may be less than or about 20% of the amount of native oxide removed. In some embodiments the amount of sidewall materials, such as liners, barriers, or spacers, may be removed less than or about 15%, less than or about 10%, less than or about 5% less than or about 3% less than or about 1% of the amount of native oxide removed, or the sidewall materials may be substantially or essentially maintained. Similarly, the amount of hard mask removed may be less than or about 100% of the amount of native oxide removed, and may be less than or about 90%, less than or about 80%, less than or about 70%, less than or about 60%, less than or about 50%, less than or about 40%, less than or about 30%, less than or about 20%, less than or about 10%, less than or about 5% of the amount of native oxide removed, or less.

Turning to FIGS. 5A-5C is illustrated cross-sectional views of a semiconductor substrate on which operations of the present technology are being performed. FIG. 5A illustrates a formation process that may include a hard mask 505 on which polysilicon lines or mandrels 515 have been formed. Oxide spacers 510 may be positioned about the polysilicon mandrels 515. Additionally, an amount of oxide 516, which may be a native oxide formed after other operations or during vacuum break, may be formed over the polysilicon mandrels 515. Removal of the native oxide may be difficult in conventional processes without isotropically etching into the oxide spacers 510 as well as other liner or spacer material. For example, etching processes as discussed previously that may occur at lower temperatures may isotropically etch through native oxide 516, but may also remove or attack oxide spacer 510. This may reduce the critical dimension of such features to a degree that may affect device operation or other downstream operations.

FIG. 5B illustrates aspects of an etching method according to the present technology. For example, an inert plasma may be formed within a processing region of a semiconductor processing chamber. The inert plasma may produce effluents 520 that are directed to the surface of the semiconductor substrate and the exposed materials thereon. These effluents of the inert plasma 520 may be used to modify an exposed portion of silicon oxide, such as native oxide 516, on the semiconductor substrate within the processing region of the semiconductor processing chamber. The plasma may be a bias plasma formed from hydrogen (H₂) or one or more other inert precursors as previously described. The power level of the bias plasma may be less than or about 100 W, and may be around 75 W in embodiments.

The modification operation may be performed for about 10 seconds or less up to several minutes or more depending on the depth of penetration sought and the parameters of the modification. A low pressure may be maintained within the processing chamber, such as about 250 mTorr to about 300 mTorr, for example, to produce a relatively anisotropic delivery of plasma effluents 520 as illustrated. The plasma effluents may modify exposed portions of native oxide 516 as well as hard mask 505. The depth of penetration may be limited to about 1 nm in embodiments, but may extend to a depth of about 2 nm, about 3 nm, about 4 nm, about 5 nm, or more.

Operations may include forming a plasma of a fluorine-containing precursor in a remote region of the semiconductor processing chamber, where the remote region may be separated from the processing region of the semiconductor processing chamber by a showerhead. The modified regions of hard mask 405 and native oxide 516 may be contacted with plasma effluents of the fluorine-containing precursor. Etching with the plasma effluents may be performed on the modified silicon oxide, and the temperature of the substrate or chamber during the etching may be about 90° C., which may allow etching of the modified layers while limiting or preventing etching of the unmodified regions of each material underlying the modified portions. Additionally, because the etching operations may be performed at about 90° C., limited solid byproducts, or no solid byproducts, may be produced during the etching operations. As shown in FIG. 5C, these operations may fully remove the native oxide about the polysilicon mandrels while having a limited removal of hard mask material 505. It is to be understood that FIG. 5C is intended only as an illustration of the process, and does not necessarily accurately show the depth of etching. FIG. 5C may show an exaggerated profile of the hard mask for the sake of illustration of the methods according to the present technology. Although not shown, additional processes may be performed within the chamber, such as chamber 200 to further remove the silicon mandrels 515. By adjusting chemistry and process characteristics, the operations may all be performed in a single chamber in embodiments.

The plasma effluents used in the etching operations may be formed in a remote region of the semiconductor processing chamber fluidly coupled with, and physically separated from, the processing region of the semiconductor processing chamber. Thus, the remote region of the semiconductor processing chamber may be a region defined within the semiconductor processing chamber. Additionally, the remote region of the semiconductor processing chamber may be a region external to the semiconductor processing chamber, but fluidly coupled with an inlet to the semiconductor processing chamber. For example, the fluorine-containing plasma effluents may be produced in a remote plasma unit coupled with the semiconductor processing chamber. Either of these configurations may prevent or reduce sputtering at the wafer level during the etching, and reduce contaminant deposition or production within the processing region.

The plasma effluents of the fluorine-containing precursor may be produced by a capacitively-coupled plasma in embodiments, or may be produced by an inductively-coupled plasma, or other plasma generating process. The power level of the plasma may be less than or about 1000 W in embodiments, and may be less than or about 900 W, less than or about 800 W, less than or about 700 W, less than or about 600 W, less than or about 500 W, less than or about 400 W, less than or about 300 W, less than or about 200 W, less than or about 100 W, less than or about 75 W, or less than or about 50 W. For example, the power level may be about 75 W to control plasma dissociation of the materials, which may provide additional control over the etching characteristics such as by, for example, not fully dissociating all fluorine-containing precursors used in the operations. However, in embodiments full dissociation may be desired, and higher plasma power levels may be used.

The precursors used in the etching operations of the modified silicon oxide may additionally include a hydrogen-containing precursor, that may also contact the modified materials. The hydrogen-containing precursor may be included with the fluorine-containing precursor to produce plasma effluents of all precursors. The hydrogen-containing precursor may also bypass the remote region of the semiconductor processing chamber in embodiments. For example, the hydrogen-containing precursor may be delivered to the processing chamber at a port or channel downstream from the remote plasma generation. The hydrogen-containing precursor may interact with the plasma effluents of the fluorine-containing precursor subsequent to the plasma effluents of the fluorine-containing precursor exiting the remote region of the semiconductor processing chamber in embodiments.

The etching performed on the modified portions of the semiconductor substrate may be performed in a way to limit the removal of unmodified material underlying the modified material, or separate from the unwanted material, such as the native oxide. As previously discussed, the temperature at which the etching is performed may affect whether the unmodified material is etched once exposed, or to what degree it is etched. The material modification and removal operations discussed throughout the present disclosure were shown in examples to be capable of performing the entire removal of materials illustrated from FIG. 5A-5C. Almost infinite selectivity for modified silicon oxide was produced in the discussed methods, and virtually infinite or infinite selectivity of modified silicon oxide to unmodified silicon oxide may allow the removal of discrete regions of silicon oxide, such as native oxide, from substrate surfaces even with other unmodified regions of silicon oxide on the substrate, such as liners, barriers, or spacers. The temperature during the removal operation may be maintained above about 80° C., which may contribute to the etching operation removing no or minimal unmodified material. As the processing temperatures is reduced below about 100° C. to about 80° C. or lower, and more so below about 50° C., the underlying, unmodified portions may etch as well, reducing the efficiency of the treatment, and possibly preventing suitable outcomes of material removal.

In the preceding description, for the purposes of explanation, numerous details have been set forth in order to provide an understanding of various embodiments of the present technology. It will be apparent to one skilled in the art, however, that certain embodiments may be practiced without some of these details, or with additional details.

Having disclosed several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the embodiments. Additionally, a number of well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present technology. Accordingly, the above description should not be taken as limiting the scope of the technology.

Where a range of values is provided, it is understood that each intervening value, to the smallest fraction of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Any narrower range between any stated values or unstated intervening values in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of those smaller ranges may independently be included or excluded in the range, and each range where either, neither, or both limits are included in the smaller ranges is also encompassed within the technology, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly dictates otherwise. Thus, for example, reference to “a layer” includes a plurality of such layers, and reference to “the precursor” includes reference to one or more precursors and equivalents thereof known to those skilled in the art, and so forth.

Also, the words “comprise(s)”, “comprising”, “contain(s)”, “containing”, “include(s)”, and “including”, when used in this specification and in the following claims, are intended to specify the presence of stated features, integers, components, or operations, but they do not preclude the presence or addition of one or more other features, integers, components, operations, acts, or groups. 

The invention claimed is:
 1. An etching method comprising: generating an inert plasma from an inert precursor within a processing region of a semiconductor processing chamber; modifying a surface of an exposed material on a semiconductor substrate within the processing region of the semiconductor processing chamber with effluents of the inert plasma; subsequent the modifying, forming a remote plasma from a fluorine-containing precursor to produce plasma effluents; flowing the plasma effluents to the processing region of the semiconductor processing chamber with a hydrogen-containing precursor that has bypassed the remote plasma; removing the modified surface of the exposed material from the semiconductor substrate with the plasma effluents of the fluorine-containing precursor; and annealing modified material remaining subsequent the etching operation, wherein the annealing comprises contacting the modified material with an inert gas heated to a temperature above a temperature of the substrate.
 2. The etching method of claim 1, wherein the inert plasma comprises a hydrogen plasma.
 3. The etching method of claim 1, wherein the inert plasma is formed from a bias power below about 100 W.
 4. The etching method of claim 1, wherein the surface of the exposed material on the semiconductor substrate is modified to a depth from the exposed surface within the semiconductor substrate of less than about 5 nm.
 5. The etching method of claim 1, wherein a pressure within the semiconductor processing chamber while forming the inert plasma and during the modifying is maintained below about 500 mTorr.
 6. The etching method of claim 1, wherein the remote plasma is formed in a region of the semiconductor processing chamber fluidly isolated from the processing region of the semiconductor processing chamber or is formed in a remote plasma unit fluidly coupled with the semiconductor processing chamber.
 7. The etching method of claim 1, wherein the exposed material on the semiconductor substrate comprises an oxide material located proximate a polysilicon material positioned along the semiconductor substrate.
 8. The etching method of claim 1, wherein each operation of the etching method is repeated in at least one additional cycle, and wherein a total removal after all cycles is less than 10 nm.
 9. The etching method of claim 1, wherein the semiconductor substrate is maintained at a temperature above or about 80° C. during the removal of the modified surface of the exposed material.
 10. The etching method of claim 9, wherein removing the modified surface of the exposed material exposes an unmodified portion of the material, and wherein an etching selectivity of a modified portion of the material to the unmodified portion of the material is greater than or about 100:1.
 11. An etching method comprising: igniting an inert plasma within a processing region of a semiconductor processing chamber; modifying an exposed region of silicon oxide on a semiconductor substrate within the processing region of the semiconductor processing chamber with effluents of the inert plasma; subsequent the modifying, forming a plasma of a fluorine-containing precursor to produce plasma effluents, wherein the plasma of the fluorine-containing precursor is formed remotely from the processing region of the semiconductor processing chamber; contacting the modified silicon oxide with plasma effluents of a fluorine-containing precursor; etching the modified silicon oxide, wherein the modifying, contacting, and etching are all performed in the semiconductor processing chamber, and wherein the etching is performed at a temperature above about 70° C.; and annealing modified silicon oxide remaining subsequent the etching operation, wherein the annealing comprises contacting the modified silicon oxide with an inert gas heated to a temperature above a temperature of the substrate.
 12. The etching method of claim 11, wherein the etching is performed at a temperature of about 90° C.
 13. The etching method of claim 11, wherein the plasma effluents of the fluorine-containing precursor are formed in a remote region of the semiconductor processing chamber fluidly coupled with, and physically separated from, the processing region of the semiconductor processing chamber.
 14. The etching method of claim 13, wherein the plasma effluents of the fluorine-containing precursor are produced by a capacitively-coupled plasma at a power level of less than or about 100 W.
 15. The etching method of claim 13, wherein the modified silicon oxide is additionally contacted with a hydrogen-containing precursor.
 16. The etching method of claim 15, wherein the hydrogen-containing precursor bypasses the remote region of the semiconductor processing chamber, and wherein the hydrogen-containing precursor interacts with the plasma effluents of the fluorine-containing precursor subsequent to the plasma effluents of the fluorine-containing precursor exiting the remote region of the semiconductor processing chamber.
 17. An etching method comprising: forming an inert plasma within a processing region of a semiconductor processing chamber, wherein the inert plasma comprises a hydrogen plasma formed by a bias power of less than 100 W; modifying an exposed region of silicon oxide on a semiconductor substrate within the processing region of the semiconductor processing chamber with effluents of the inert plasma, wherein the exposed region of silicon oxide comprises a material positioned about a silicon mandrel, wherein a pressure within the semiconductor processing chamber is maintained below about 1 Torr during the modifying; forming a plasma of a fluorine-containing precursor in a remote region of the semiconductor processing chamber that is separated from the processing region of the semiconductor processing chamber by a showerhead; contacting the modified silicon oxide with plasma effluents of the fluorine-containing precursor; and etching the modified silicon oxide at a temperature of about 90° C., wherein the modifying, contacting, and etching are all performed in the semiconductor processing chamber, and wherein no solid byproducts are produced during the etching.
 18. The etching method of claim 17, wherein the remote region of the semiconductor processing chamber is a region defined within the semiconductor processing chamber.
 19. The etching method of claim 17, further comprising annealing modified silicon oxide remaining subsequent the etching operation, wherein the annealing comprises contacting the modified silicon oxide with an inert gas heated to a temperature above a temperature of the substrate. 